Thermodynamique des mélanges liquides binaires. Chaleurs de mélange des cycloalcanes

Heats of mixing were measured between 10° and 80°C for all binary systems formed with cycloalcanes C_nH_2n, n = 5, 6, 7, 8.     

Thermodynamique des mélanges liquides binaires. Volume de mélange d'alcanes normaux et ramifies

Volumes of mixing were determined by dilatometric measurements between 15° and 50°C for isomeric alkanes with n-hexadecane and n-dodecane. The negative excess volumes vary linearly with temperature.     

Propriétés themodynamiques des mélanges binaires. Chaleurs de mélange des n-alcanes ainsi que de leurs isomères

The following heats of mixing have been measured: the five isomers of hexane with n-dodecane at 10°, 20° and 30°C, and with n-hexadecane at 20°C, as well as the systems dodecane-hexene-1 at 20°C, and dodecane-methyl-2-pentene-1 at 10° 20° and 30°C.     

Thermodynamique des mélanges liquides binaires. Volume de mélange et nombre moyen de configurations gauches des alcanes

It is shown that there exists a fair correlation between the average number of ‘gauche’ conformations of normal and branched alkanes, and their volumes of mixing.     

Étude thermochimique des méthylnaphtalènes

Calorimetric measurements of enthalpies of change of state (sublimation or vaporization) of methylnaphthalenes gave the following results:

1-methylnaphthalene: (ΔH√_vap)_m=(57.32±0.42) kJ mol⁻¹

2-methylnaphthalene: (ΔH√_sub)_m=(65.69±0.84) kJ mol⁻¹

Combination of these values with those obtained by Speros and Rossini¹ for enthalpies of combustion of these compounds makes it possible to determine their energy of isomerization more accurately. This energy is (2.97±2.41) kJ mol⁻¹ and should be attributed to steric hindrance in the 1-methylnaphthalene molecule.

The comparison of energies of conjugation, theoretical as well as experimental, which we have determine for both molecules studied, confirms the present result.     

Etude comparative des méthyl-borazines par RMN

A comparative study of borazine ( 0 ) and six methyl borazines ( 1 to 6 ) has been conducted by NMR. It becomes evident that the chemical shift of N? CH₃ protons hardly varies between mono-, di- and tri-N-methyl borazines, whereas this parameter undergoes a strong change (in all 0·21 ppm, to high field) when one passes from N-trimethyl borazine (HB? NCH₃)₃ to hexamethyl borazine (CH₃B? NCH₃)₃ through a gradual substitution on the three boron atoms ( 3, 4, 5 and 6 ). Moreover, a systematic variation of the parameter δ has been found between compounds 3, 4 and 5 for the protons which keep precisely the same immediate environment. A qualitative interpretation of this experimental result is proposed in terms of electronic effects general to the hexagonal planar boron/nitrogen ring which characterises these molecules.     

Sur l'acylation des métylfuorènes I. Benzoylation et acétylation du méthyl-1-fluorène

Benzoylation and acetylation of 1-methylfluorene according Friedel-Crafts in carbon disulfide with aluminium chloride yielded the corresponding 2-acyl derivatives. By oxydation the benzoyl derivative gave 2-benzoyl-9-oxo-fluorene-1-carboxylic acid, cyclizable into 1,2-phthalyl-fluorenone.     

Le mécanisme de l'hydrolyse acide des aryl-diazométhanes

In the acid catalysed hydrolysis of three monoaryl-diazomethanes (p)-nitrophenyl-diazométhane (I), p-chlorophenyl-diazomethane (II), phenyl-diazomethane (III), absence of exchange H-D, solvent isotope effects about 2,6, and general acid catalysis prove that proton transfer is rate determining (A-S_E2 mechanism). Like other A-S_E2 reactions, the hydrolysis of I is shown to obey the Brønsted catalysis law with a variety of carboxylic acids; for eight of these acids, α_B was found to be 0,69 ± 0,06.     

Sur l'acylation des méthylfluorènes VI. Formylation du méthyl-2-fluorène et du méthyl-3-fluorène selon Rieche

The formylation of 2-methylfluorene and of 3-methylfluorene according Rieche yields 2-methyl-7-fluorene-carbaldehyde and 3-methyl-2-fluorenecarbaldehyde respectively. The constitution of the obtained aldehydes is proved by their conversion into the known 2,7-dimethyl-fluorene and 2,7-dimethyl-9-fluorenone, respectively into the known 2,3-dimethylfluorene and 2,3-dimethyl-9-fluorenone.     

Sur l'acylation des méthylfluorènes IV. [1] Benzoylation du méthyl-4-fluorène

Benzoylation of 4-methylfluorene according to Friedel-Crafts in carbon disulfide with aluminium chloride yielded two benzoyl derivatives: 5-methyl-2-benzoyl-fluorene (II) (major product), and 4-methyl-2-benzoyl-fluorene (III). By oxidation II and III gave the corresponding 9-oxo-derivatives, the structure of the last compounds being proved by an independent way.     

Stabilité des carboxylates de terres,III. Maléates,méthylsuccinates et malates

The stability constants of maleates, methylsuccinates and malates of rare earths have been determined at 25.0 °C and at ionic strength 0,100 (NaClO₄) by a potentiometric method. Each ligand forms 1 : 1 and 1 : 2 complexes in aqueous solution, the malates being the most stable. The first and the second dissociation constants of the ligand acids were also measured. The 1 : 2 maleates of La, Pr, Nd, Sm, and Eu have been isolated.     

Action d'organolithiens sur la méthyl-2 quinoxaline. Etude de la réactivité des adduits

The action of organolithium reagents such as phenyllithium or n-bulyllithium on 2-methylquinoxaline gave lithiation of the methyl group which upon reaction with electtropholesphiles produce side chain alkenyl derivatives. On the other hand organolithium reagents react with the quinoxaline azomethine bond to give I-lithio-2-alkyl)or ary-1)-3 methylquinoxalines which can be further loithiated on the methyl group to give 2-alkyl(or aryl)-3-alkenylquinoxaline derivatives. The adducts can be condensed with clectrophiles such as benzonitrile or methlyl benzoate but only methyl benzoate leads to N condensed derivatives. Furthermore substituted 1,2,3,4-terahydroqinoxalines are available via the above lithio intermediates.     

Nouvelle méthode de détermination des taux de réativité des copolymères par résonance magnétique nucléaire: Application aux poly(méthacrylate de méthyle–chlorure de vinylidène)

Constant-composition copolymers of methyl methacrylate and vinylidene chloride produced by radical copolymerization are studied by ¹H-NMR at 60 and 250 MHz. The different methods of the literature for the derivation of reactivity ratios from either the copolymer composition or the sequence average lengths, or even the diad distribution, are applied but lead to rather dispersed results. A new graphical method is proposed, based on the use of peculiar values of the triad distribution functions. It allows us to detect a penultimate effect for the vinylidene chloride-rich region. In the same range, a change in tacticity of the diads and triads on the methylmethacrylate sequences, as compared with homopolymers, is observed; it suggests that the anomaly is caused by the competition of the depropagation reaction.     

Stabilité dans le méthanol et propriétés thermodynamiques de transfert des cryptates de certains cations de transition et de métaux lourds

Stability in Methanol and Thermodynamic Transfer Properties of the Cryptates of some Transition Cations and Heavy Metals The nature and stability of the macrocyclic and macrobicyclic complexes of Ag⁺, Cd²⁺, and Pb²⁺ (Mⁿ⁺) with 21, 22, 211, 221 and 222 in anhydrous methanol 0.05M in Et₄N⁺ClO^?₄, at 25° (see Scheme) have been determined by potentiometry and spectrophotometry. Binuclear complexes M₂L²ⁿ⁺ have been observed in all cases, besides the mononuclear MLⁿ⁺ complexes. The macrobicyclic 1:1 complexes MLⁿ⁺ exhibit an important ‘cryptate effect’ with Mⁿ⁺=Ag⁺, Pb²⁺ and Cd²⁺, but not with Cu²⁺ and Zn²⁺; their stability is in all cases maximum with 221. The applicability to our results of the recent extrathermodynamic hypothesis involving MLⁿ⁺ cryptates is examined.     

Calorimètre pour la mesure des chaleurs de mélange des liquides

A calorimeter has been designed for measuring the heat of mixing of liquid systems, which eliminates the need to correct for changes in the composition of the vapour phase on mixing. Improved accuracy has been obtained. It permits the measurements of thermic effects of the order of 0.005 joule, corresponding to temperature differences of 10^?4 of a degree. Heats of mixing have been measured for the system hexadecane-hexane, the results of which are highly satisfactory.     

Etude des mécanismes de réarrangement dans la fragmentation des benzoyloxy-cyclopentànes par impact électronique

The fragmentation modes of 3-benzoyloxy-cyclopentene and of 4-benzoyloxy-cyclopentene have been studied on deuterium-labelled analogues. A mathematical model is proposed for the study of the rearrangement reactions which occur during the expulsion of H₂O and of \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CO}_2 {\rm H}^. $\end{document} from the molecular ion of 3-benzoyloxy-cyclopentene.     

Polymérisation anionique du méthacrylate de méthyle par les organo-alcalins-I : Polymérisation en milieu solvant aprotonique, étude des tacticités

Anionic polymerizations of methylmethacrylate, initiated by fluorenyl-alkali metals in ether media or in hexamethyl phosphotriamide, give syndiotactic polymers. Calculated differential entropies and enthalpies of activation between the iso- and syndiotactic placements reveal that in dioxane, tetrahydropyrane and tetrahydrofurane the syndiotacticity increases from K⁺ to Li⁺. With solvents having higher dielectric constant (such as hexamethyl phosphotriamide) or higher donating power (such as glyme 4), the tacticity of the polymers is not affected by the nature of the counter-ions.

It has been suggested that, with dioxane, tetrahydropyrane and tetrahydrofurane, the donating power is not strong enough to destroy the coordination bonds between the C=O groups of the living polymer chains and the counter-ions.     

Sur l'acylation des méthylfluorènes II [1]. Benzoylation et acétylation du méthyl-2-fluorène

Benzoylation and acetylation of 2-methyl-fluorene according of Friedel-Crafts in carbon disulfide with aluminium chloride yielded the corresponding 7-acylderivatives. By oxydation the benzoyl derivative gave 7-benzoyl-9-oxo-fluorene-2-carboxylic acid, which was decarboxylated to the known 2-benzoyl-9-oxo-fluorene. By reduction according to Clemmensen the acetyl derivative gave 2-methyl-7-ethylfluorene.     

Sur l'acylation des méthylfluorènes III [1]: Benzoylation et acétylation du méthyl-3-fluorène

Benzoylation and acétylation of 3-methyl-fluorene according to Friedel-Crafts in carbon disulfide with aluminium chloride yielded the corresponding 2-acyl derivatives. By oxidation the benzoyl derivative gave 2-benzoyl-9-oxo-fluorene-3-carboxylic acid, cychsable into the known 2,3-phthalyl-fluorenone. By Clemmensen reduction, the acetyl derivative gave 3-methyl-2-ethyl-fluorene.